KTm[B4O6(OH)4] ⋅ 3H2O: A New Member of Borate Family with Mica-like Tetrahedral Layers

Crystallography Reports - Crystals of new borate KTm[B4O6(OH)4] ? 3H2O (sp. gr. Р $$\bar {3}$$ 1m, a = 4.5472(7) Å, c = 12.151(3) Å) have been obtained under hydrothermal...     

New rubidium pentaborate Rb[B5O7(OH)2] · 0.5H2O with a 5: [4Δ + 1T] anionic block and its relation to larderellite (NH4)[B5O7(OH)2] · H2O on the basis of the OD theory

A new rubidium pentaborate is synthesized under hydrothermal conditions. Its crystal structure is studied by the heavy-atom method without any a priori knowledge of chemical formula. The chemical formula is Rb[B₅O₆(OH)₄] · 0.5H₂O, sp. gr. $\bar P1$ , lattice parameters a = 7.679(4) Å, b = 9.253(6) Å, c = 12.053(9) Å, α = 98.55(5)°, β = 106.80(5)°, γ = 91.71°, R = 0.0573, R _w = 0.0638, S = 1.07. The anionic part of the structure consists of a chain of fundamental building blocks 5:[4Δ + 1T] built by four B triangles bound to one B tetrahedron, which are common to Na, K, Rb, and Cs pentaborates. This new pentaborate is closely related to the mineral larderellite (NH₄)[B₅O₆(OH)₄] · H₂O but possesses an original structure, which manifests itself in the different morphology of the new pentaborate and the absence of perfect cleavage. The Dornberger-Schiff OD theory allows one to describe in detail the structural relationships, predict possible hypothetical structures, and write the OD groupoid.     

Crystal structure of tri-μ-carbonyl-pentacarbonyl {diphenyl-2-pyridylphosphine-(P,N)} bis {diphenyl-2-pyridylphosphine-(P)} tetrairidium (0), [Ir4(CO)8(PPh2pyl)3]

The structure of the title tetranuclear cluster, C₅₉H₄₂N₃O₈P₃Ir₄, was determined by X-ray analysis. It crystallizes in the monoclinic space groupC2/c. The unit cell parameters are:a =47.277(6),b=10.519(3),c=23.025(4) Å, =105.77(1)°. The iridium atoms form a nearly regular tetrahedron. Between Ir4 and N336 atoms exists a relatively strong bond, thus one of the phosphine ligands is bridging one coordinatingvia P and N atoms.     

Hydrothermal crystallization and X-ray structure determination of a new decavanadate with mixed cations [Mn(H2O)6]2[N(CH3)4]2[V10O28]·2H2O

A new decavanadate with mixed cations, [Mn(H₂O)₆]₂[N(CH₃)₄]₂[V₁₀O₂₈]·2H₂O (1), was crystallized from a hydrothermal reaction between MnCO₃ and V₂O₅ in the presence of N(CH₃)₄Br at 100°C. The structure of 1, as determined by x-ray single crystal analysis, consists of cations and anions of hexa-aqua manganese [Mn(H₂O)₆]²⁺, tetramethyl ammonium [N(CH₃)₄]⁺ and decavanadate [V₁₀O₂₈]^6–. The extended H-bonding between the [Mn(H₂O)₆]²⁺ and [V₁₀O₂₈]^6– ions gives rise to a pseudo- two-dimensional network in the crystal lattice x-ray crystallographic data for 1: monoclinic P2₁/n, a = 9.1499(5), b = 12.8725(7), c = 18.625(1) Å, = 92.252(1)°, V = 2192.0(2) ų, MZ = 2, and D _calcd = 2.22 g cm^–3.     

Architecture of phosphates with {[L 2(PO4)3] p−}3∞ frameworks

The general principles of the structural organization for the existing types of orthophosphates with the {[L ₂(PO₄)₃] ^p?}_3∞ frameworks, where L is an octahedrally coordinated ion, are discussed. Representing these frameworks by double LP₆-octahedra, it is possible to find out the related structures and analyze their symmetry relation.     

Tiettaite K4Na12Fe3+Si16O41(OH)4 ⋅ 2H2O: A Mineral with a Novel Type of Microporous Heteropolyhedral Framework

Crystallography Reports - Microporous silicate tiettaite from the Khibiny alkaline massif (Kola Peninsula, Russia) has been studied using X-ray diffraction analysis, electron probe microanalysis,...     

Low-temperature X-ray studies of a [(CH3)2NH2]2 · CuCl4 crystal

The a, b, c lattice parameters of a [(CH₃)₂NH₂]₂ · CuCl₄ crystal have been measured by the X-ray diffraction method within the temperature range of 100–300 K. The temperature dependences of thermal expansion coefficients α_a = f(T), α_b = f(T), and α_c = f(T) along the principal crystallographic axes and thermal expansion coefficient of the unit-cell volume αV = f(T) are determined. It is found that all the three parameters, a, b, and c, vary with temperature in a complicated way and show jumplike anomalies in the a = f(T), b = f(T), and c = f(T) curves at phase-transition temperatures T _c1 = 255 K and T _c2 = 279 K. An incommensurate phase with the modulation wave vector q _i = (1/2 + δ)(a* + c*) is revealed in the temperature range 279–296 K. It is shown that the incommensurability parameter δ increases with an increase in temperature.     

Structure of the adduct of bis(O,O′-diisopropyldithiophosphato) metal with pyridine: Ni[(iPrO)2PS2]2(py)2 and Cd[(iPrO)2PS2]2 (py)2(py = pyridine)

The crystal and molecular structures of the complex of [Ni{(iPrO)₂dtp}₂(py)₂] and [Cd{(iPrO)₂dtp}₂(py)₂] (dtp = dithiophosphate, py = pyridine) have been determined by X-ray crystallography. They are isomorphous. The crystal structures are very similar and consist of discrete molecules of [Ni{(iPrO)₂dtp}₂(py)₂] and [Cd{(iPrO)₂dtp}₂(py)₂], respectively. They both crystallize in the monoclinic system, space group P2₁/c, the former with lattice parameters a = 6.489(1) Å, b = 14.830(3) Å, c = 16.386(3) Å, = 99.74(3), and Z = 2; the latter with a = 6.461(3) Å, b = 14.583(4) Å, c = 17.433(4) Å, = 99.55(3)°, and Z = 2. They all display distorted octahedral geometry around the central metal atom. In the complexes, two O,O-diisopropyl dithiophosphate ions act as bidentate ligands with their S atoms coordinated to metal. Each forms a four-membered chelate ring in the equatorial plane. The N atoms from two pyridine ligands are axially coordinated to the metal atom. The Ni–S bond distances are 2.5137(10) and 2.5386(9) Å, and the Ni–N bond distances are 2.127(3) Å. The Cd–S(1) and Cd–S(2) bond distance are 2.694(1) and 2.704(1) Å, respectively, and the Cd–N bond distances are 2.399(3) Å. The IR spectra data is in agreement with the structural data.     

Crystal structure ofcis-[Ru(bpy)2{PPh2(o-tol)}Cl][ClO4]·1.5(CH2Cl2), a structure containing both ordered and disordered dichloromethane molecules of crystallization

The complexcis-[Ru(bpy)₂ {PPh₂(o-tol)}Cl][ClO₄] crystallizes from dichloromethane as the sesqui-dichloromethane solvate. The complex crystallizes in the monoclinic space group P2₁/n with Z=4. The structure was refined toR=5.50% for those 2552 independent reflections with |F ₀|>6(|F ₀|) The octahedral Ru(II) cation is associated with the following bond lengths: Ru-PPh₂(o-tol)=2.360(3)Å. Ru–Cl=2.433(2)Å and Ru–N(bpy)=2.041(8)–2.095(8)Å. Both the perchlorate anion and the dichloromethane molecules of solvation exhibit large amplitudes of vibration. One dichloromethane molecule lies in a general position, the other lies about an inversion center and suffers from disorder.     

Reactions of [Mn2(μ-pyS)2(CO)6] with bidentate phosphines: X-ray structure of [Mn(η2-pyS) (η2-dppp)(CO)2] [dppp = Ph2P(CH2)3PPh2, pySH = pyridine-2-thiol]

The dimeric complex [Mn₂(-pyS)₂(CO)₆] (1) reacted with 2 molar equivalents of Ph₂P(CH₂)₃PPh₂ (dppp) and Ph₂P(CH₂)₂PPh₂ (dppe) to give the respective monomeric chelate complexes [Mn(²-pyS)(²-dppp)(CO)₂] (2) and [Mn(²-pyS)(²-dppe)(CO)₂] (3). In contrast, with 2 molar equivalents of Ph₂P(CH₂)₅PPh₂ (dpppe), 1 gave the highly insoluble polymeric complex [Mn(²-pyS)(-dpppe)(CO)₂]n (4). An X-ray structure determination shows that 2 crystallizes in the monoclinic space group P2₁/n with a = 10.721(2) Å, b = 19.712(5) Å, c = 14.846(4) Å, = 109.06(2)°, V = 2965.5(14) ų, and Z = 4. The complex has a distorted octahedral geometry with the dppp ligand, one CO group and the N atom of the chelating pyS ligand occupying equatorial sites, and one CO group and the S atom of the pyS ligand lying in the axial positions.     

Crystal structure of (4α,4aα,8aα)-(±)-octahydro-2-(phenylmethyl)-2H-1,2-benzoxazin-4-ol, 4-methylbenzenesulfonate(ester)

The title compound, a bicyclic tetrahydro-1,2-oxazine, crystallizes in a monoclinic lattice, space group P2₁/c, with a = 12.9809(18)Å, b = 12.920(2)Å, c = 13.631(2)Å, = 110.713(12)°, and Z = 4. The structure found in the solid state for this conformationally mobile molecule shows the tosyl group in an axial position and a benzyl group in an equatorial position of the bicyclic system.     

Synthesis and physicochemical characterization of a porous coordination polymer of Sn-Cu xylarate: The structure of [Sn4Cu8.5(HL)2(L)4O2(OH)(H2O)12.5] · 17.2H2O

A porous coordination polymer of Sn-Cu xylarate [Sn₄Cu_8.5(HL)₂(L)₄O₂(OH)(H₂O)_12.5] · 17.2H₂O (H₅ L is xylaric acid) is synthesized for the first time and characterized by chemical analysis, IR spectroscopy, and X-ray diffraction. Centrosymmetric heterometallic fragments [Sn₄Cu₆(HL)₂(L)₄O₂(H₂O)₆] (A) including copper Cu1–3 and tin Sn1,2 atoms are distinguished in the structure. The Cu4(OH)_0.5(H₂O)_2.5 bridges connect A units into chains running along the c axis, and the Cu5(OH)(H₂O) bridges connect A fragments into layers perpendicular to the c axis. The Cu4,5 atoms form a framework whose voids accommodate the crystallization water molecules.     

Geometrical model of the structure of the heterocomplex compound [Cr(OCN2H4)6]3+[Co(DH)2(NO2)2] 3 − ⋅ 2H2O

The structural organization of the new heterocomplex compound with carbamide has been considered on the basis of division of the crystal space into Dirichlet polyhedra of the system of Delone points (centers of the complex ions). It is demonstrated that the coordination numbers for all domains (Dirichlet domains) of the complex ions in the structure obey the “rule of fourteen,” whereas the polyhedra providing the structural organization of the crystal are distorted Fedorov cuboctahedra.     

New Cluster Precursors—K5 Pyramids and K4 Tetrahedra—for Self-Assembly of Crystal Structures of Mn4(ThMn4)(Mn4)-tI26, Mn4(CeCo4)(Co4)-tI26, and MoNi4-tI10 Families

Crystallography Reports - A combinatorial and topological analysis has been performed, and the self-assembly of the crystal structures of the Mn4(ThMn4)(Mn4)-tI26 (sp. gr. I4/mmm),...     

Synthesis and crystal structure of bis(carbamide)chromatoneptunyl NpO2CrO4 · 2[OC(NH2)2]

The crystal structure of the hexavalent neptunium complex NpO₂CrO₄ · 2[OC(NH₂)₂] is determined. The crystal data are a = 7.192(2) Å, b = 12.902(4) Å, c = 11.226(3) Å, β = 92.19(2)°, V = 1040.9(4) ų, space group P2₁/n, Z = 4, d _calcd = 3.223 g/cm³, R = 0.045, and R _w = 0.130. The coordination polyhedron of the Np atom is the pentagonal bipyramid whose equatorial plane is formed by the oxygen atoms of the chromate ions and carbamide molecules.     

Crystal and molecular structure of [Cu2(3,5-dihydroxybenzoate)4 (acetonitrile)2] ⋅ 8H2O

The crystal and molecular structure of the title compound, [Cu₂(3,5-dihydroxybenzoate)₄ (acetonitrile)₂] 8H₂O 1, is reported. Crystal data for 1: tetragonal, space group I 4/m, a = 11.720(2) Å, c = 15.304(3) Å, V = 2102.4(6), and D _c = 1.53 g/cm³, for Z = 2. The metal and organic components crystallize to form a Cu paddle-wheel complex, of idealized D_4h symmetry, that assembles in the solid-state, along with eight equivalents of water, to form a 3D hydrogen-bonded network held together by O–H O hydrogens bonds. The metal complexes pack to form a 2D layered structure.     

Synthesis and structural characterization of [VS4(CuPPh3)4Br]·CH2Cl2

Heating a solid mixture of (NH₄)₃VS₄, CuCl, PPh₃, and NEt₄Br at 100°C for 10 h and extraction with CH₂Cl₂ yielded [VS₄(CuPPh₃)₄Br]·CH₂Cl₂. Crystallographic data: Triclinic, P1¯, a = 15.189(3), b = 20.093(6), c = 12.031(3) Å, = 102.39(2), = 100.05(2), = 82.86(2)°, V = 3517(3) ų, and Z = 2. The configuration of the VS₄Cu₄Br core can be described as a distorted cubane with an additional face. The V atom has retained the tetrahedral geometry of the free [VS₄]^3– moiety. The four Cu atoms have three different coordination environments, strongly distorted tetrahedral, nearly trigonal planar, and strictly trigonal planar. The infrared, electronic, and ⁵¹V NMR spectra have also been reported.